Triazine dyes



Patented Oct. 23, 1956 United States PatentOfi r 2,768,158

' i This mono condensation product is then condensed with 2 a 8 8 I 1 mole of .a second amino azo dye like 4-amino azoben= zene. This secondary condensation product of cyanuric TRIAZINE DYES chloride with the 2-amino mono azo dyes is condensed I i 5 finally with aniline. The product so obtained is coupled Fredelflhk strobe]! phflhpsbm'g Land wflham alkaline with diazotized H acid. As another example,

WllSOIl Williams, Easton, Pa., asslgnors to General e & Film Corporation, New York N. Y. a cop 4,4 -d1am1no stilbene-2,2 -disulfon1c acid is condensed Duration of Delaware first with 2 moles of cy'anuric chloride to give the di- V condensation product: No Drawing. ApplicationMarch 30, I953, 10

Serial No. 345,732 C1 t c 6Claims. c1.z60-1ss) H; H 803E H 5 N o-N o=c- N-Cf N This invention relates to triazine dyes for cotton con- 15 taining the carbamyl hydrazide group or its imido or g I l thio analogue. V Y 01 It is common practice in synthesizing dyes from cyanuric chloride to carry out the third or finalcondensation (elimination of the active halogen atoms) with aniline. Thus, for example, cyanuric chloride is made to react first with one mole of an amino containing azo com- 20 i This product is then condensed with 2v moles of the amino monoazo dye:

This product is then condensed with 2 moles of aniline to give the final dye:

4 above is subjected to an AATCC wash test without aftertreating with the copper salt mixture, it is not as fast to The above dyes are but two examples of a host of dyes which have been derived from cyanuric chloride in which the third or final condensation of the active halogen is washing as cloth similarly treated with dye (B) above. made to aniline. Other amines have been reported in the Also, when cloth dyed with dye (A) above is afterfinal condensation, for instance, N-methyl'aniline (U. S. 5 treated with copper sulfate only, and then subjected to Patent 2,301,333, page 4, Example 5) and methyl amine an AATCC No. 3 wash test, the dyed cloth is inferior in (U. S. Patent 2,399,066, page 2, Example 5). fastness to the cloth similarly treated with the dye (B) Most of the dyes of the cyanuric chloride type are apabove. Thus, it would appear that some specific interplied to cotton or regenerated cellulose. It is standard action or chemical reaction occurred between the practice to after-treat direct cotton dyes with a product e which is essentially a mixture of a copper salt (copper H sulfate) and partially polymerized cyano guanidine- N N C NH formaldehyde. The dyed cloth after-treated is somewhat group of dye (A) and the more wash-fast than the untreated dyed cloth. NH

We have discovered that dyes derived from cyanuric chloride in which the third active halogen atom of the cyanuric chloride is condensed with guanyl hydrazine,

H II NCNCNHz-l-H:C O

polymer of the copper salt mixture. In this connection, semicarbazide or thiosemicarbazide, show even superior it is a s ignifi ant that When amines other than aniline Wet-fastness (Washing) following after-treatment with the w r used as third o ing agent with y n h10- copper salt mixture, to dyes in which the third active fideythe wash-fastfless Was no'heflel' than vthat 0f the halogen atom of the cyanuric chloride is condensed with ye prepared from aniline after treating the dyed cloth aniline or other such amines. Thus, for example, if the With the PP P Y miXtllfe- Thus, it has been two dyestuffs: found that when morpholine, monomethylamine, mono- HOOC 00011 HaC- (ii-43H H-C-CHI N =0 O= N N N H H hydroxyethylamine, N-methylaniline, dihydroxyethylamine, a.-naphthylamine, phenyl hydrazine, N-methyl anthranilic acid, and the like, are used in place of aniline are separately dyed on cotton cloth by the usual direct dyeing application and the dyed cloth treated with the copper salt polymer mixture, the cloth dyed with dye (A) shows markedly superior fastness to washing in an as third condensing component with cyanuric chloride, AATCC wash test No. 3 than does the cloth dyed with the dyeings are not superior in AATCC wash test No. 3 dye (B). to the dye (B) above when the copper salt polymer mix- The reason for the foregoing unusual and unexpected ture after-treatment is used. behavior is not clearly understood. It is believed, how- Moreover, we further discovered that when dyestuffs ever, that the following explanation, based upon experiderived from diamino disulfostilbene, as described in mental observations may shed some light on the unusual U. S. Patent 2,399,066 and triazine dyes containing and unexpected phenomenon: When cloth dyed with (A) pyrazolone rings as described in U. S. Patent 2,301,333,

including those illustrated above, wherein the final condensation is made with one of the following compounds:

Thiosemicarbazide dyestufis are obtained which are superior in Wash fastness to the dye (B) illustrated above. It appears that the beneficial action-of the mixture of copper sulfate and partially polymerized 'cyano guanidine-formaldehyde, and similar mixtures currently available to textile printers, in improving the wash fastness of dyes containing any one of the foregoing guanylhydrazide, semicarbazide, or lthiosem'icarbazi'de is specific. It is possible to account for the behavior of the cyano guanidine-formaldehyde improvement by postulating a condensation of the hydroxymethyl residue of the aforementioned copper salt polymer mixture, with the semicarbazido, thiosemicarbaz'ido and iminosemicarbazido end of the dye molecule. This interpretation is ofiered merely as a possible explanation of the unusual and uneXpected-effectof the dyestuffs involved in the present invention.

Accordingly, it is the object of the present invention to provide triazine dyes containing in one or two triazine nuclei a group characterized by the following formula:

wherein R represents 0, S, or NH.

The dyestufls provided by the present invention are derived, as described above, from cyanuric chloride in which one halogen atom of the cyanuric chloride is condensed with either ,B-guanylhydrazide, semicarbazide, or

thiosemicarbazide, and are characterized by the following formulae:

OH; H

4- [3'-carboxy-4'-hydroxy phenylazo 1 -phenyl 3. O 0 OH OH O O H 3-carboxy-4- [2,4'-hydroxy-5'-carboxy-phenyl-azo] -pheny1 5. C OOH H l G ir O=C\ /N $0 OH I 1. 50311 SO3H Sti1bene-2,2-disulfonic acid-4,4-diamino S 0 :H S 0 3H Diphenyl-3,3-disulfonic acid-4,4"-diami uo O OH Dipheny1-3,3'-dicarboxylic ac1d-4,4-diamino Diphenylamine-S-sulfonic acid-4,4-diamino 5. N80 35 S 0 3N3 Diphenylenesulfone-3,3'-disu1fonic acid (sodio salt)-4,4'- diamino HOOCHzC HCHzOOOH Diphenyl-3,3-dicarboxy-methoxy) -4,4'-diamin0 7. COONa COONa Ga -RG Dlphenylurea-B,3-dicarboxylic acid (sodio sa1t)-4,4-diamino SOzH S Dlphenylurea-3,3-disu1fonic acid-4,4'-diamino COOH CODE Diphenylthiourea-3,3-dicarboxy1ic acid-4,4'-diamino Example 1 43.3 grams of S-nitroanthranilic acid was slurried with 1500 ml. of water and then heated to 65 C. To the solution were added 56 ml. of 30% aqueous sodium nitrite. The resulting solution was maintained at 65 C. and it was dripped into a mixture of 72 ml. of cone. HCl and 150 ml. of water previously cooled to C. The amine acid was added in 40 minutes maintaining a temperature of C. by adding 200 grams of ice. After all had been added, the mixture was stirred for 1 hour at 13 C., then clarified by filtration from a small amount of precipitate. The excess of nitrite was removed by the addition of 5 ml. of 10% amine-sulfonic acid. Meanwhile a coupler solution was prepared by adding 23.4 grams of 3-methyl-5-pyrazolone to 200 ml. of water, heating to 70 C. and treated with 20.5 ml. of 40% aqueous caustic soda. The solution was cooled to 25 C.; pH=9.0. This pyrazolone solution was then diluted to 250 ml. by volume. It was added gradually to the diazo solution above. 77 ml. of '4 N-sodium acetate were added. Coupling was complete in 2 hours. The material was filtered and dried.

The dried product weighed 61.2 grams and amounted to an 87.6% yield. The reduction of the final product with sodium sulfide was accomplished by slurrying onehalf of the dried product with 500 ml. of water and 10 ml. of 40% aqueous sodium hydroxide. To the slurry 36.5 grams of sodium sulfide were added and the slurry heated to 59 C. The temperature rose to 65 C. At

this point, the heated mixture turned dark red in 5 minutes and black in 10 minutes. The mixture was stirred for 3 hours at 60-66 C., then cooled to room temperature and treated with 27 ml. of glacial acetic acid. A precipitate resulted which was filtered off. The filtrate was acidified with 50 ml. of concentrated hydrochloric acid and the heavy precipitate which formed was filtered 01f. The resulting presscake was reslurried in 350 ml. of water, treated with 10 ml. of 40% aqueous sodium hydroxide, heated to C. and filtered to remove the sulfur precipitate. The filtrate was then cooled to 5 C. and the solid product removed by filtration and dried.

The monoazo dye intermediate prepared as above was utilized in the preparation of the dyestufi having the formula designated by (A) by the following procedure:

16 grams of 4,4'-diamino-2,2-disulfostilbene were dissolved in 250 ml. of water and 25 ml. of 20% sodium carbonate on a steam bath, then cooled to 0 C. 14.2 grams of cyanuric chloride was dissolved in 60 ml. of acetone CP by heating to 35 C. (slight residue remained). This solution was poured into the diamine solution containing some excess ice at a temperature of l-4 C. The pH was 6.7 to 7.0. For 20 minutes the temperature was maintained at 2 C. with a pH of 6.8. 0.531 N caustic soda was added from a burette to neutralize the acid liberated in the reaction. 142 ml. of 0.531 N sodium hydroxide were added in 50 minutes, keeping the pH at 5.5 to 6.5. The test for free amine by coupling became negative. Total time for first condensation was 100 minutes.

22.5 grams of the monoazo dye prepared as above were dissolved on the steam bath in 750 ml. of water, cooled to 60 C., then poured on 600 grams of ice. No precipitate appeared. The first condensation product pre' pared above was poured into that solution of monoazo dye. No precipitate appeared. The temperature rose to 8 C. 78 ml. of 0.531 N caustic soda were added from a burette in 10 minutes bringing the pH to 7.0. The temperature was kept at 815 C. for 1 hour. A gelatinous mass formed. 51.6 ml. more of 0.531 N sodium hydroxide were added bringing the pH to 10.3. The material was heated to 40 C. in 20 minutes. The pH dropped in this time from 10.3 to 9.5. Temperature was held at 45 C. and in 30 minutes the pH became 6.7. 8 ml. more of sodium hydroxide solution were added bringing the pH to 7.4. Five hours after beginning the second condensation, the test for free amine was negative and the pH was 6.9. The material was allowed to stand overnight. The pH was 6.7 in the morning. For the third condensation, 10.5 grams of guanyl hydrazine bicarbonate were slurried with 20 ml. of water and then treated with 70 ml. of 3.7% hydrochloric acid. This acid solution was then added to the second condensation product at 27 C. The pH became 6.0. 157 ml. of 0.531 N sodium hydroxide were added from a burette (equal to an amount necessary to neutralize 70 ml. of 3.7% hydrochloric acid to a pH of 7.0), and the pH rose from 6.8 to 10.9. The material was heated to C. in 40 minutes and then kept at this temperature for 100 minutes. The pH dropped to 10.2. 136 ml. more of 0.531 N sodium hydroxide were added in 25 minutes. The pH rose to 11.3. The volume was about 3.5 liters and was kept at this value by water addition. The material was reheated to 70 C. and the pH was 9.8. 0.5 gram of fl-guanylhydrazine bicarbonate was added, the temperature raised to C., and maintained at 95 C. for 4 /2 hours. The pH dropped from 9.8 to 8.6. 80 ml. of 20% sodium carbonate were added and the material heated at 95 C. for /2 hour. The slurry was cooled to room temperature and filtered. The presscake was packed down and dried in a vacuum oven at 80 C. The dried product weighed 48.5 grams. The dye so prepared dyed cotton an orange-yellow shade, which on after-treatment with the copper salt polymer mixture was rendered fast to light and washing.

Example The above dyestufi was prepared b the procedure of the example of U. S. Patent 2,041,829 with the exception that 25 grams of ,B-guanylhydrazide were used in place of 30 grams of aniline.

0.2 mole of the sodium salt of 1 acid having the following formula:

NtlOgS NH:

was added to a slurry of 18.3 grams of cyanuric chloride (0.1 mole) in 500 ml. of water. To this slurry at 10 C. there were added over a period of 1 hour 20 ml. of 40% sodium hydroxide, and the solution brought essentially to neutral at the end of 2 hours. The free amine test for I acid (self coupling) had disappeared at the end of this time. Then there are added grams of semicarbazide, and the material is heated to 95 C. for 4 hours. At the end of this time there is added a slurry of 0.2 mole of the diazo of 2-amino phenol 4-sulfonic acid prepared in the usual manner. To the mixture of triazine compound and diazo there is added 200 ml. of sodium carbonate solution (wt/vol.) and the mixture is stirred until the test for free diazo disappears (2 hours). 'The precipitate of dye is salted out, filtered, Washed with "5% salt solution, and dried in a vacuum oven at 90 C. The dyestutf is reslurried in 500 ml. of water, and treated with acetic acid until the pH is 6.5. Then there were added 65 grams of copper sulfate and the dye-slurry and copper sulfate stirred for 48 hours at room temperature. The mixture was evaporated at 80 C. to a thick paste, and finally dried in the vacuum oven at 125 C. for 1 day to give the final dyestufl, which dyes cotton a rubine shade.

Example-4 Example 2 was repeated with the exception that grams of fi-guanylhydrazide were replaced by 25 grams of thiosemicarbazide.

SOtH

OsH

Example 5 Example 1 was repeated with the exception that 1 05 grams of [i-guanylhydrazide were replaced by 25 grams of thiosemicaroazide.

Example 6 Example I was again repeated With-the exception that 10.5 .;grams of fl-guanylhydra-zide were replaced by 10.5 grams of semicarbazide.

Example 7 Example 3 was repeated with the exception that 15 grams of semicarbazide were replaced by 15 grams of B-guanylth-iosemicarbazide.

All of the dyes of the foregoing examples, including the dyestufi illustrated by designation (B), the dyestutf of the example of U. S. Patent 2,041,829 and a prepared dyestuif of Example 3 in which the semicarbazide is replaced by an anilino group, were employed in dyeing cotton skeins. The skein dyeing (10 grams of cotton skein) containing 0.1 gram of each one of the said dyes was after-treated with 0.2 gram of the copper salt polymer mixture in 300 ml. of water for 20 minutes at F., removing the skein, rinsing and drying. The dyed samples in which the dyestufi is devoid of the aforementioned guanyl components became yellower and duller on after-treatment.

Each of the dyed and after-treated samples was subjected to the AATCC wash test No. 3. The samples in which the dyestutf is devoid of the aforementioned guanyl components were very poor in wash "fastness, whereas those samples dyed with the dystufls containing the same components were exceptionally fast.

While there have been pointed out above certain preferred embodiments of the invention, the same is not limited to the foregoing examples, illustrations, or to the specific details given therein, but is capable of variations and modifications as to the reactants, proportions, and conditions employed.

We claim:

1. A triazine dye characterized by a formula selected from the class consisting of the following formulae:

and

wherein R represents a member selected from the class consisting of O, S, and NH; R1 represents a mono azo dye radical selected from the class consisting of 3-carboxy-4-[3'-methyl-5-0Xo-4'-pyrazolyl-azo]-phenyl, 4-[3- carboxy 4' hydroxy-phenylazo] phenyl, 3-carboxy-4- [2,4'-dihydroxy-5'-carboxy-phenylazo]-phenyl, 3-sulfo-4- [1-phenyl-3'-methyl-5'-oxo-4-pyrazolyl-azo] phenyl, 3- carboxy 4-[1-phenyl-3-methyl-5-oxo-4'pyrazolyl-azo] phenyl, 3-carboxy-4-[3 sulfocarbanilino l acetonylazo]-phenyl, and 2-chloro-4-E1'hydroxy-3'-sulfo-2'-naphthyl-azo] -5hydroxy phenyl radicals; and R2 represents a diaryl diamino radical selected from the class consisting of stilbene-2,2'-disulfonic acid-4,4-diamino, diphenyl- 3,3-disulfonic acid-4,4-diamino, diphenyl-3,3'-dicarboxylic acid-4,4-diarnino, diphenylamine-3-sulfonic acid-4,4- diamino, diphenylenesulfone-3,3'disulfonic acid (sodium salt)-4,4'-diamino, diphenyl 3,3 di(carboxy-methoxy)- 4,4'-dia1nino, diphenylurea-3,3'-dicarboxylic acid (sodium salt)-4,4'-diamino, diphenylurea-3,3'-disulfonic acid-4,4- diamino and diphenylthiourea 3,3 dicarboxylic acid- 4,4'-diamino radicals.

2. A triazine dye characterized by the following formula:

3. A triazine dye characterized by the following for- I IH OH HO C H; l

HOaS SOQH OCH:

4. A triazine dye characterized by the following formula:

13 14 6. A triazine dye characterized by the following formula:

References Cited in the file of this patent UNITED STATES PATENTS 2,270,478 Schmid Ian. 20, 1942 2,295,565 DAlelio et al. Sept. 15, 1942 2,399,066 Schmid et a] Apr. 23, 1946 2,537,834 Kaiser et a1. Jan. 9, 1951 

1. A TRIAZINE DYE CHARACTERIZED BY THE A FORMULA SELECTED FROM THE CLASS CONSISTING OF THE FOLLOWING FORMULAE: 